Oxyethylated hydrophile derivatives of certain fractional esters of triricinolein



Patented Nov. 27, 1951 OXYETHYLATED HYDROPHILE DERIVA- TIVES or CERTAINFRACTIONAL ES- TERS or 'riimrcmousm Melvin De Groote, University City,and Bernhard Keiser, Webster Groves.- Mo., assignors to PetroliteCorporation, Ltd., Wilmington, Del., a corporation of Delaware NoDrawing. Application May 29, 1948, Serial No. 30,186

6 Claims. 1

This invention relates to a new chemical product or compound and to themanufacture of same, our present application being acontinuation-in-part of our co-pending application Serial No. 758,487,filed July 1, 1947, now abandoned, which was in turn, a division of ourco-pending application Serial No. 666,819, filed May 2, 1946, nowabandoned.

Complementary to the above aspect of our invention is our companioninvention concerned with the new chemical products or compounds used asdemulsifying agents in the resolution of water-in-oil emulsions,particularly petroleum emulsions, as described in our co-pendingapplication Serial No. 30,188 filed May 29, 1948, now Patent 2,498,658,granted February 28, 1950.

The new products herein described are also useful as wetting, detergentand leveling agents in the laundry, textile and dyeing industries; aswetting agents and detergents in the acid washing of fruit; in the acidwashing of building stone and brick; as wetting agents and spreaders inthe application of asphalt in road building and the like, as aconstituent of soldering flux preparations; as a flotation reagent inthe flotation separation of various aqueoussuspensions containingnegatively charged particles such as sewage, coal washing waste water,and various trade wastes and the like; as germicides, insecticides.emulsifying agents, as, for example, for cosmetics, spray oils,water-repellent textile finishes; as lubricants, etc.

Briefly stated, the new compounds herein contemplated, and which, inaddition to being particularly desirable as demulsifying agents forpetroleum emulsions of the water-in-oil type, but are also useful forother purposes, are derived by the oxyethylation of certain acidicfractional esters of triricinolein. Such acidic esters are obtained byreacting triricinolein with one to three moles of polycarboxy acid, andparticularly a dicarboxy acid such as phthalic acid, adipic acid,diglycollic acid, etc. The hereto appended claims are limited toderivatives of dicarboxy acids oranhydrides.

Acidic esters of triricinolein can be manufac-'- tured in two difierentways, although using the same general procedure. One method is to useThe second procedure radical may be attached to the glyceryl radical andnot limited to attachment to the ricinoleyl radical. This latter type ofstructure will be clarified by subsequent description. It is to benoted, however, that the compounds contemplated herein are thoseobtained from intermediates in which the dicarboxy acid radical isattached to the ricinoleyl radical, and thus excludes acidic estersobtained by rearrangement at higher temperatures, or in presence ofcatalysts.

The manufacture of fractional esters of triricinolein is well known anddescribed in numerous patents. The literature including various patents,also describes the esteriflcation of such fractional esters withpolyhydric alcohols including polyglycols under various conditionsinvolving, for example, either the presence or absence of catalysts, ora variety of catalysts, including both acid and basic catalysts.

It has been suggested that the reaction of a fractional ester with apolyethylene glycol under various conditions would, in essence, resultin a product substantially the same as that obtained by reacting withethylene oxide, so as to obtain the same stoichiometric relationship. Wehave found that this is not the case and that the resultant products aresignificantly different in composition, and those products obtained byoxyethylation are much more effective, for a number of purposes, suchas, for example, demulsification of petroleum emulsions, break inducers,in the doctor treatment of sour hydrocarbons, etc.

Since this difference in composition involves the inherent nature of thereactants and resultants, it is deemed desirable to point out clearlythe nature of the product obtained when triricinolein is reacted withpolycarboxy acids, and particularly those having 4 to 10 carbon atoms,and particularly dicarboxy acids having 4 to 8 carbon atoms, such assuccinic acid, adipic acid, diglycolic acid and phthalic acid. Theanhydrides, of course, are the abvious equivalent of the acid andinclude among others phthalic anhydride, maleic anhydride, citraconicanhydride, etc. Other suitable acids include maleic, fumaric, oxalic,tricarballylic, tartaric, azelaic, sebacic, etc. Other acids includecisA -tetrahydrophthalic anhydride obtained by the action of butadieneon maleic anhydride, and 3,6-endomethyleneM-tetrahydrophthalic anhydrideobtained by the action of cyclopentadiene on maleic anhydride. It is tobe noted that none of these acids have more than 10 carbon atoms. Asstated, it is understood that the acids and anhydrides are considered asequivalents.

A preferred ester product may be obtained by esterification reactionbetween triricinolein and a dibasic carboxylic acid such as phthalicacid.

Ricinoleic acid may be indicated by the following formula:

on CH3(CH2)5.41H.CH2.CHCH(CH2)7.COOH

which may be conveniently abbreviated for many purposes to HORCOOHEmployin HORCOO as the acyloxy group of ricinoleic acid, triricinoleinmay be represented by the formula HO RC 0 CH2 HORCOOCH HORCOO Hz andcontains the residue of the polyhydric alcohol glycerol, which may berepresented as HOCHE H0 H HO(.I7H2' Trirlcinolein readily esterifieswith phthallc acid, and if three moles of phthalic anhydride or acid arecaused'toreact with one mole of triricinolein, a fractional acidic esterwill be obtained according to the following reaction:

CO noacooom 3 0 noaooocn coon COORCOO H COOH COORCOO Hi It is notnecessary to use three moles of phthalic anhydride per mole oftriricinolein, and if desired, onemay use one or two moles, although thepreference is to use approximately 2 to 2%; or 3 moles.

Likewise, in carrying on the esterification reactions broadly, withoutlimitation to the particular type herein employed as intermediates, itis not essential that a carboxylic group'of the .dibasic carboxylic acidreact with the alcoholiform hydroxyl in the ricinoleyl radical While thericinoleyl radical remains directly connected with the polyhydricalcohol radical. One might react ricinoleic acid monophthalate, obtainedby reaction between ricinoleic acid andphthalic anhydride, mole formole, with glycerol, in-the ratio of three'moles of the fractional ester.for one mole otglycerol. This would yield a mixture of compounds suchasthe following:

HOOCROO OOCH:

HOOCROO; 00 H HOOCROO; 00 H:

HOOCROO 00011: HO-OCROO (BOO H H0O; OORCOO Hz HOOCROO} OOCH: H003 OORCOOHr H006 OORCOO Ha Not only may compounds of the above type be obtainedby the procedure previously described, but such compounds may-occur to agreater or lesser degree, as the result of molecular rearrangement inthe production of acidic fractional esters from triricinolein andvarious polycarboxy acids, as previously mentioned, provided one employstemperatures in excess of 210 C. or employs catalysts, or both.

In carrying on the esterification reaction, there may developcross-linkages either through the polyhydric alcohol, or through thepolybasic carboxylic acid, due to the polyfunctionality of thesematerials; For example, in an esterification reaction betweentriricinolein and phthalic acid, the resulting product may comprise morecomplex molecules, such as the following, which illustratescross-linkage through the polyhydric alcohol residue. I

C; HzCOOCROO 00H H OOCROO OOH so I I HzQOOCROO OORGOO-CH:

HO; OORCOOCH:

HORCOO H OOORCOOJJHz COORCOOOHz HORCOO H H00? (IJOORCOO E:

It is apparent that other cross-linkages may occur. Such ester productscontaining more complex molecules are also suitable. It is also apparentthat there may be great variations-in the molecular weight of theproduct. The molecular weight of the ester product, as determined bycryoscopic methods, or from obvious composition of the ester, usuallyruns between about 300 and about 4,000 and is seldom over 6,000. Esterproducts having a molecular weight over about 10,000 preferably are notemployed. During the esterification reaction there may be somepolymerization and polymerized products, as well as simple monomers, maybe used. Attention is directed to what has been said previously for thesake of clarification, and that is that the intermediates hereincontemplated, i. e., the acidic esters derived by reaction betweentriricinolein and various dicarboxy acids or anhydrides, are limited tothose obtained by manufacture under conditions which preclude drasticrearrangements, and thus, are characterized by the fact that thedicarboxy acid radical is attached directly to the ricinoleyl radicaland not to the glyceryl radical.

Tricarboxy acids may be employed as reactants in the same manner asdicarboxy acids.

However, it is obvious, in light of what is said subsequently, that if atricarboxy acid is used, subsequent oxyethylation results in a branchedchain or two chains of polyglycol radicals instead of one. In otherWords, if a dicarboxy acid,,su ch as phthalic acid, is employed, thereis a single carboxyl radical available for oxyethylation. If, on theother hand, tricarballylic acid is employed, then there may be, and inmost instances, there happens to be, two carboxyls available foroxyethylation, thus resulting in either a branched chain or two separatepolyglycol radicals. Actually, the configuration so produced from astructural standpoint, closely approximates that ob-- tained by treatinga sole carboxyl radical remaining from phthalic acid with glycide orglycerol and then oxyethylating such ester so as to obtain a branchedchain polyglycol or two separate polyglycol radicals. Since this type ofcompound is contemplated in our co-pending application Serial No.30,187, filed May 29, 1948, now Patent 2,498,657, granted February 28,1950, it will be noted that the specific examples herein included andthe claims themselves are directed to derivatives of dicarboxy acids.

TRIRICILNOLEIN ACIDIC 'FRACTIONAL ESTERS Example 1 One pound mole oftriricinolein (in the form of castor oil which ordinarily containsapproximately to triricinolein) is reacted-with.

2 pound moles of phthalic anhydride to produce a mixture of acidphthalates consisting essentially of triricinolein dibasic phthalate andtriricinolein tribasic phthalate. The reaction may be caused to occur byheating the mixed materials at a temperature of approximately to C. forapproximately 6 to 12 hours. The reaction can be followed roughly bywithdrawing a small sampleof the partially reacted mass and permittingit to cool on a watch crystal. When the reaction has become completed nocrystals of phthalic anhydride appear. When the sample no longer showsthe presence of such crystals on cooling, it can be titrated with astandard volumetric alkaline solution, since the acid which remains isdue entirely to carboxylic hydrogen in the fractional ester and not toany unreacted phthalic anhydride. If care is taken not to use too hightemperatures which would cause formation of heterocyclic bodies of thecharacter above referred to, one can depend upon the standard alkalinesolution to indicate the disappearance ofthe phthalic anhydride. It isnot to be inferred, however, that any cyclic bodies, if formed, would beunsuitable.

The product thus obtained, however, seems to consist largely oftriricinolein dibasic phthalate and triricinolein tribasic phthalate.Apparently, there is no evidence of rearrangement there.

This fact is indicated by a molecular weight de termination and alsobased on the acid value which usually runs from a little over 100 toslightly less than 110.

TRIRICINOLEIN ACIDIC FRACTIONAL ESTERS Example 2 Maleic acid oranhydride is substituted for phthalic anhydride in preceding Example 1to give the corresponding maleic acid derivative, i. e., triricinoleindibasic maleate and triricinolein tribasic maleate.

TRIRICINOLEIN ACIDIC FRACTIONAL ESTERS Example 3 Adipic acid oranhydride is substituted for phthalic anhydride in preceding Example 1to give the corresponding adipic acid derivative, i. e., triricinoleindibasic adipate and triricinolein tribasic adipate.

TRIRICINOLEIN ACIDIC FRACTIONAL ESTERS Example 4 succinic acid oranhydride is substituted for phthalic anhydride, in preceding Example 1,to give the corresponding succinic acid derivative, i. e., triricinoleindibasic succinate and triricinolein tribasic succinate.

TRIRICINOLEIN ACIDIC FRACTIONAL ESTERS Example 5 7 resembling somewhatblown'castor' oil in consistency, and water-insoluble.

It is to be noted that the triricinolein acidic fractional esters hereincontemplated as the preferred reactants are characterized by the factthat they are obtained by esterification reactions involving the use ofat least one mole of the dicarboxy acid per mole of triricinolein. Forinstance, previous formulae indicate combinations wherein 1 moles to 3moles of phthalic anhydride are used per mole of triricinolein. In allinstances, regardless of the ratio of dicarboxy reactant totriricinolein, there must be at least one free carboxyl per mole oftriricinolein inthe finished product. Such requirement is met, ofcourse, by triricinolein monobasic phthalate derived from one mole oftriricinolein and one mole of phthalate anhydride. Attention is alsodirected to the fact that all the fractional esters are prepared in.such a manner that the final product is anhydrous. The next step is theobvious one of subjecting such anhydrous ester to the action of ethyleneoxide.

If one examines the formula for ricinoleic acid,

'it becomes obvious that the dicarboxy acid, such as phthalic acid,becomes attached approximately half-way in the carbon atom chain, andthus oxyethylation attacking any residual carboxyl group which is partof the dicarboxy acid radical, must, of necessity, cause the hydrophilepolyglycol group to enter or make its effectiveness felt halfway in thecarbon atom chain, as differentiated with the introduction of ahydrophile group at the end of a carbon atom chain. For instance, when ahigh molal alcohol or a high molal acid is subjected to oxyethylation,obviously such hydrophile effect is produced terminally and not at amid-point. In this connection it is interesting to note thatoxyethylation does not, as was one time believed, attack the secondaryalcohol of triricinolein when castor oil is subjected to oxyethylation.For this reason, oxyethylation of the fractional esters give a producthaving a hydrophobe-hydrophile balance, which is entirely different fromthat obtained from a number of apparently kindred products. Genericallyspeaking, oxyethylation is conducted in substantially the same manner asapplied to a number of other products, in which the ethylene oxide groupis introduced between an oxygen atom and a hydrogen atom, as, forexample, in oxyethylation of high molal acids or high molal alcohols,substituted phenols, etc. Usually a small amount of alkaline catalyst isadded, such as one-tenth of 1% to 1% of caustic soda, sodium stearate,sodium methylate, or the like. Oxyethylation is conducted with constantstirring and a gauge pressure of 100 to 200 pounds per square-inch isgenerally satisfactory. The temperature of reaction may be varied from100C. to less than 200 C. If desired, an inert solvent may be presentsuch as xylene, tetralin, cymene, decalin or the like. The ethyleneoxide may be used continuously, provided the addition is regulated sothat it is used up more or less uniformly as it enters the reactionvessel or autoclave. Our preference, however, is to add the materialbatch-wise, as indicated, and continue oxyethylation not only until theproduct is distinctly hydrophile but until it gives a substantiallyclear solution in water. As to other oxyethylating procedure, attentionis directed to the following United States patents and to the followingBritish patent: U. S. Patent Nos. 2,142,007, dated December 27, 1938, P.Schlack; 1,845,198, dated February '16, 1932, O. Schmidt et al.; and1,922,459, dated August 12, 1933, O. Schmidtet al.; and British PatentNo; 302,041, dated August 7, 1928, James Y. Johnson.

WATER-SOLUBLE OXYETHYLATED TRIRI- CINOLEIN ACIDIC FRACTIONAL ESTERExample 1 650 pounds of triricinolein acidic fractional estermanufactured as described under the heading Example 1, preceding, ismixed with one-half pound of sodium methylate and then reacted withapproximately 161 pounds of ethyleneoxide in three batches of 53.7pounds each. The maximum pressure during the reaction was pounds persquare inch gauge pressure. The time of reaction required for each batchwas three to five hours. The temperature employed was approximately C.The material was tested for water-solubility after the addition of 161pounds of ethylene oxide and found to be water-insoluble. If thetheoretical molecular weight of triricinolein tribasic phthalate isconsidered as 1.450, then the average molecular weight of the rawmaterial employed was taken as 1300. On this basis, the amount ofethylene oxide added at this point represented a molal ratio of 1 to7.3, approximately.

Oxyethylation was then continued by the addition of three more portionsof approximately 68 pounds each so that at the end of the sixth batchthe molecular ratio had more than doubled and was approximately 1 to18.0. The product at this point began to show some distinctly hydrophilecharacter and solubility, but was reacted further with five additionalportions of approximately 65 pounds each. Thus, the total amount ofethylene oxide added represented 161 pounds, plus pounds, plus 325poundsbeing a total of 666 pounds of ethylene oxide added to 650 poundsof the original resin. On a weight basis this represented slightly inexcess of '1 to 1, and on a molal basis it represented approximately 30to 32 moles of ethylene oxide per mole of monomeric fractional ester.The resultant product was a thin, deep amber-colored oil, watersoluble,having a clear appearance in solution and some foaming properties. a

The product so obtained consists principally of oxyethylatedtriricinolein dibasic phthalate and oxyethylated triricinolein tribasicphthalate. The composition of these two compounds may be shown in thefollowing manner:

COORCOOCHZ COORCOOCH:

HORCOO H COORCOOL /H @CPC? WATER-SOLUBLE OXYETIV-IYLATED .TRIRI-CINOLEIN ACIDIC FRACTIONAL ESTER Example 2 The same procedure isfollowed as in Example 1, immediately preceding, except that trlricinolein acidic fractional esters, Examples 2 to 5, inclusive, aresubstituted for triricinolein acidic fractional ester, Example 1. Ineach instance ethylene oxide is added in the same molecular proportion,i. .e.,.approximately 30 to 32 moles of ethylene oxide per mole permixture averaging about 2 molesof dicarboxy acid per mole oftriricinolein. In all instances the molecular weight is figured-based onthe theoretical combination of the dicarboxy reactant and triricinoleinwithout the loss of any water in the case of the anhydride andwith thelossof only one molecule of water per molecule of dicarboxy acid, in-theevent an acid reactant such as diglycollic acid or adipic acid is usedinsteadof an anhydride. However, the proportions by weight mayubeemployed just as satisfactorily, i. e., adding'enough ethyleneoxide sothat itis approximately equalin weight of the acidic ester.

WATERASOLUBLE OXYETHYLATED TRIRI- CINOLEIN ACIDIC FRACTIONAL ESTERExample 3 WATER-SOLUBLE OXYETHYLATED TRIRI CINOLEIN ACIDIC FRACTIONALESTER Example 4 The same procedure is followed as in Examples 1 and 2,preceding, except that the amount of ethylene oxide added was increasedper batch, so that the total amount is equal to approximately 40 moles,instead of 24 or 32 moles, and is equal in weight to approximately 125%of the original atom, whether the hydroxyl; be. a carboxylic hydroxyl oran alcoholichydroxyl, as shown by the previous examples where a carboxylradical is converted first into a glycol esterandlthen subsequently intoa polyglycol ester. This means,

of course, that if the triricinolein acidic fractional esters had beenreacted with ethylene oxide or propylene oxide or butylene oxide, molefor mole, so as to give a hydroxylated ester in;

stead of an acidic ester, such hydroxylated 'ester woul'd be just-as'lsusceptible ;to oxyethyla aortas" the acidic ester? In -"other words;an iii- 1G termediate step in'the previously described'reace tionsrepresent compounds exemplified byrthe following:

0 O OCZHlOH --COORCOOCH2 COORCOO H2 Compounds of the above type couldalso be obtained by esterifying the free carboxyls with a glycol such asethylene glycol, propylene glycol, etc. It is understood, however, thatthis particular specification does not include those types wherein suchglycols would be replaced by polyhydric alcohols having a larger numberof hydroxyl groups per molecule, 1. e., does not include glycerol,diglycerol, triglycerol, etc. Furthermore, the compoundsherein'contemplated are derived solely from triricinolein and do notinclude compounds derived from monoricinolein, diricinolein, or anyother type of fractional ester where the number of ricinoleic acidradicals is less than the valency of the polyhydric alcohol (theglyceryl radical) to which they are attached. Valency of the radical insuch circumstances is measured by the number of availablehydroxylgroups, i. e., the valency of a glyceryl radical be ing considered as 3.The reason for this difference is perfectly obvious, in that anavailable glyeeryl hydroxyl radical, as in the case of, a derivative ofmonoricinolein or diricinolein, provides an additional point of reactionfor a polybasic acid, such as phthalic anhydride, or if not so reactedupon, provides a point of reaction for ethylene oxide. Similarly, if theacidic esters are esterified with glycide or methylglycide instead ofethylene oxide or the like, or glycerol for that matter, then suchesters are capable of attack by ethylene oxide so as to provide abranched chain, rather than a single chain' involving polyglycolradicals. What has been said herein immediately preceding is intended todefine the herein contemplated compounds with greater clarity and alsoto point out the line of demarcation between these particular compoundsand those contemplated in our abandoned copending application Serial No.666,820, filed May 2, 1946. f Products of value as demulsifying agentshave been prepared by reacting triricinolein phthalates of the kinddescribed under the heading Triricinolein Acidic Fractional Esters withpolyhydric alcohols, although not necessarily with polyethylene glycolshaving a large number of repetitious ether linkages in such proportionand manner as to render such fractional esters Water-soluble orwater-miscible. At first casual examination, it would appear that if onewere to react the acid phthalates, as exemplified by Triricin'oleinAcidic Fractional Esters, Example 1 with polyethyleneglycol representingapproximately 10 or 12 ethylene oxide units, there should be obtained aproduct approximately identical with the product, described under theheading Water-Soluble Oxyethylated Triricinolein acidic FractionalEster, Example 1. For instance,'the

nei'

COOH

COORCOOCH:

GOOH

COOH

COORCOO Ha ooonoooom nwnlonnooc teem-e a 31120 "o ooR-oo-olm'*ooownnoynn The above reaction emphasizes this very important feature,that if an attempt is made to obtain similar products by reaction with apoly 'e'thyleneglycol, then water results rromthe reac= um andcognizance must be taken of the fact. Thus, if the reaction is conductedin th e presence of water, whereas, oxyethylation is conducted underanhydrous conditions, then one must bear in mind that the water formedmay become a reactant before elimination. Hence, it isobvious that thecourse of reaction may be changed.

Another courseof difference in the reaction in vowing etliy1ene'oxide onthe one hand and a polyethylene glycol on the other, is this articularsituation; the esters employed are poly functional having, for example,preferably two or more carboxyls per original molecule of tri=-ricin'olein. The polyethyleneglycols are difunctional. Thus, whenreacted together,-there is a tendency to form a sub-resinous polyesterby reactions involving simultaneously one moleo'f a polyethylene glycoland two carboxyls, which are part of tlie same molecules or much moreprobable parts of two difierent molecules.

0 con oboncooom o 0 one o 0" H2 electorate 06H H OOCROO OH it connect(500 -1100031 wherein HOCzH r- -X CaI-IaOI-I represents the originalpolyethyleneglycol.

In connection with what is said herein, in re gard to the 'd-ifierencebetween ,oxyethylation, on the one hand, and'esteri'fication on theother hand, it mustbe-rememb'ered that oxyethylation takes'pl'acereadily and rapidly; at temperatures considerably under 200 C. and thatthis particu lar temperature may be considered the upper limit.Esterification, such as is shown subsequently, invariably involves muchhigher temperatures, such as 230 to'340 C.

An examination of such esterification reactions are best conducted on alaboratory scale. In other words, if one were to start withap roximately650 g-rams of the mixturedescribed under'the heading TriricinoleinFractional Ester, Example 1 having an acid value of approximately andadd thereto the equivalent of 2 /2 moles of a .po-lyethyleneglycolhaving approximately 10 to 1-1 structural units on completion ofreaction, one would anticipate that there would be a drop in acid valueto approximately zero, corresponding to the acid value of the productdescribed under the heading Water-Soluble Oxyethylated TriricinoleinFractional Ester, along with the elimination of a stoich'iometric'alamount of water which would be equivalent to 2 moles or 17 grains.

Such reaction can be conducted in any one of three ways: (a) Absence ofa catalyst; (b) lp're'senee of an acid catalyst, or (0') presence of abasic teata1yst. Actually, there is little or no justification for usinga basic catalyst, for the' reason that under such circumstances, onewould not expect to obtain a product comparable to that described underthe heading Water- Soluble Oxyethylatd 'Triricinolein Fractional Ester,Example 1, but would expect to get a product in which a large degree ofglycerol had been replaced by the 'nonaethyleneglycol with subsequentcorresponding freaction. In. other words, one would expecttran's-esterification, which is sometimes referred to asester-interchange or alcoholy'sis. "(See Organic Chemistry, .Fieser andFieser, 1'94 4, page 1182 and Organic Chemistry, Fuson and Snyder, 1942page 92.)

conducting these exploratory experiments it becomes obvious that the'two end points not coincide, -i. e., the elimination oithe theoreti calamountof water of reaction {and reductionpf the acidity to the value of1 or 2. In each instance an attempt was made to carry the reaction tothe end point indicated in both ways. In the case of the acid catalystone-half percent of para-toluene sulfonic acid was added. Inconnectionwith the polyethyleneglycol reactant attention is directed tothe article entitled Technology of the Polyethyleneglycols and CarbowaxCompounds, Chemical and Engineering News, 1 volume 23, No. 3, page 247(1945). Such article points out, among other things, why the value of nas herein contemplated represents an average L value, rather than'anabsolutely definite value ,of one-single compound. The result of theseexwithin the range which produces rearrangement in the manufacture ofacidic esters, as previously noted. In other words, at such temperaturerange, even though no catalysts were added, one would expectrearrangements whereby at least to a substantial extent, there would bepresent compounds in which the dicarboxy acid radical would be directlyattached to the glyceryl radical. It is to be noted that this type ofmaterial is specifically excluded in the hereto appended claims.

In light of what has been said as to the nature of the reactions takingplace and as to the results obtainedin, the above experiments, it isperfectly obvious that there is a very marked difference periments are1ndicated in the following table: in the nature of the productsobtained, depend- Experiment A Experiment B Experiment 0 L-24l42 L-24143Ill-24144 Triricinolein Fractional Ester Example 1 650 grams, Acid 650grams, Acid 650 grams, Acid I v.=l05. v.=l05. v.=l05. HO(C2H40) "H,7t=10 or 11.- rams 700 7 700. Cataly Nmw %%Toluene Sul- 36% SodiumMethfonic Acid. ylate. Acid Value of Mixture 50.5 52.0 0.2. Conditionsto bring acid value to about 2 Could not get be- Could not get be- 4hrs. at 325 0.,

low 14. low 15.6. 4 7.85 acid v. Time hnurs 3" 4 4.

Maximum temperature At this point H1O eliminated Rem ark 66.8 cc. H20and 53.4 cc. oil.

Conditions to bring about elimination of 17% gr. water (theo.).

In comparison with Experiments A, B and C, it has been pointed outpreviously in Oxyethylated Water-Soluble Triricinolein Acidic FractionalEster, Example 1 that such reactants as was used in Experiments A, B andC can be 4 treated with ethylene oxide under a comparative- 1y lowtemperature, approximately 120 C. in absence of water to give a productwhich is clearly water-soluble and which has an average molecular weightapproximately equivalent to that of the products obtained in ExperimentsA, B and C, provided there was complete chemical combination. The acidvalue of oxyethylated derivative was approximately 2. I

In Examining Experiments A, B andC, it is to be noted that it wasimpossible to reduce the acid, value in any one of the three cases tothat obtainable by oxyethylation, to wit, a value of 2. Actually, thevalues range from approximately 8 to 14. Furthermore, the theoreticalamount of water which would be expected to be eliminated in ExperimentsA, B and C so as to give a product identical withthat previouslyreferred to as Example 1, would be 17 /2 grams of water. Actually, when17 /2 grams of water had been eliminated in all three cases, the acidvalue varied from ap proximately 20 to approximately 33. On the otherhand, when the minimum acid value was obtained, even though it did notapproach the amount of 2, there was a great deal more water 55eliminated than theory; varying from 54, in one instance, to 346 in theother. Furthermore, in order to obtain the result indicated, instead ofusing a temperature of approximately 130 C. or somewhat higher, but inany event, under 200 C., the temperature actually varied from 230 C. to340 C. Attention is directed to a very significant fact, and that is,that these temperatures employed in Experiments A, B and C, as previous-13; noted, vary from 230 C. to 340 C. and are 54 cc. H20 and 15 cc. oil.

Acid v. rose on cid v. rose on further heating.

further heating.

%hour.

Time 25 min Maximum Temperature" 0.. 230 285.

Acid value at this point 36.6 20.4.

.Remar s 11; cldy. Clear oil; Cldy. Clear oil; cldy. sol.

, sol. w/water. Sol. w/water. w/water.

ing on whether an acidic fractional ester is subjected to oxyethylation,or whether it is subjected to an esterification with a polyglycol,.in anefiort to obtain substantially the same product; although, for the sakeof brevity, reference is made only to products obtained by phthalation,actually other experiments conducted with other polycarboxy acids,particularly succinic acid, adipic acid, diglycollic acid, etc.,indicate that results are substantially the same.

The difference in the nature of the products obtained by the twodifferent procedures is illustrated further by their effect uponemulsions. The following table shows results obtained by adding an equalamount of the same four materials to certain emulsions. One demulsifyingagent consists of the product described under the heading Water-Solubleoxyethylated Triricinolein Acidic Fractional Ester, Example 1, the otherthree consisting of the clear oils obtained as resultants fromExperiments A, B and C, described previously, in tabular form. Hereagain, it is to be noted that, although the results indicated areconcerned with merely one particular derivative, 1. e., phthalic acidderivatives, the results are'thes'aine as far as demulsification whenother polycarboxy acid derivatives are examined the same way. This isparticularly true of adipic acid; succinic acid, diglycollic acid, etc.

It may be desirable to point out that distillable polyglycols of thekind previously referred to and exemplified by nonaethylenegylcol or thelike, and particularly those having 8 to 12 oxyalkylated groups, aresometimes referred to as upper distillable' ethyleneglycols. (See U. S.Patent No. 2,324,489, dated July 20, 1943, to De Groote and Keiser.)

Althoughit hasbeen old to subject emulsions to emulsi yin a ents, obtaned by .r a t n' tween certain resinous products and polyhydrfc alcoholsfree from repetitious ether linkages.-yet,

as far aswe are aware, products of the kind exemplified by ExperimentsA, B and C have not been hereto prepared or employed as demulsifyingagents.

Demu'lsifying test I Date of test Oct. 30, 1945 State of California Oilfiel Oak Qanyon Oil company V. B. Wickham Lease. No.4 Well No 4 Per centemulsion in fluid from well 510 Per cent free water in fluid from wellTrace Per cent water obtained by complete dcmulsiflcatiou- 46 Per centdemulsifier in test solution 6 Temperature of tests 140 F Period ofagitation after adding .demulslfie min Nature of agitation; machine withshaker-arm, ute. 130 Ratio of demulsifier to well fluid 126700 11-2414211-24143 11-24144 L-l28fi6 Blank Time test started 2:45. cc. Water outat 26 41' Trace 33 42 Do. 37 43 Do. 38 44 Do. 40 44 Do. 41 44 Do.

Dec. 13, 1945 California Wilmington Oil company. Royalty Service LeaseSanta Fe B-2 Per cent emulsion in fluid from welL. 21.0 Per cent freewater in fluid from well Trace Per cent water obtained by completedemulsification 18.0 Per cent demulsifier in test solution 2%Temperature of tests; l. l. 160 0. Period of agitation after addingd'emulsifier 5 min.

Nature of agitatiommachine with shaker arm ;"shakes per minute 130 Ratioof demul sifier to well fluid.. lzaOOO 11-24142 L-24143 L-24144 L-12866Blank Time test started :50. cc. Water out at- 1:25 (12-13) a Trace 2: D

Per cent free Water in fluid from well Per cent water obtained bycomplete demulsification Per cent demulsifier in test solution 2Temperature of tests 160 F. Period of agitation after adding demulsifierl. 5 min.

Nature of agitation; machine with shaker arm; shakes per'minute 130Ratio of demulsifier to well fluid 1:5000

L-24l42 11-24143 L-24144 b12866 Blank Time test started 10:50. cc. waterout at Trace Trace Trace 8 Trace 2 'Trace Trace 13 Do. 3 1 Trace 14 Do.6 2 3 1 15 'Do. 7 3 4 l7 Do. 7 2 5 17 Do. 11 3 8 19 Do.

It is of considerable interest to compare compounds of the kind'hereindescribed with somewhat analogous compounds described elsewherein the literature or prepared from data appearing elsewhere. Thereagents employed, for example, ricinoleic acid, glycerol, ethyleneoxide, phthalic anhydride, etc.. can be considered as building blocks orstructural units which can be fitted together to give various compounds.Castor oil (triricinolein) may be considered as ricinoleic acid andglycerol in combination.

Some such other structures may be exemplified by examples which appearin the series of U. S. Patents Nos.v 2,295,163 through 2,295,170,inclusive, all datedpseptember 8, 1942, to De 'Groote and Keiser.Briefly stated, a'pol'yglycol acid ester such as nonaethyleneglycoldihydro'gen dimaleate, or dihydrogen diphthalate, obtained by reactionbetween one mole of nonaethyleneglycol andrtwo moles of an appropriatedicarboxyv acid or anhydride, is reacted with various hydroxylatedcompounds, including triricinolein, diricin olein, monoricin'olein, etc.

The following table briefly describes four such compounds, the firstbeing an ethylene oxide compound of the kind herein specified. In thenext three compounds, or products, an ethylene polygycol is used insteadof ethylene oxide. The compounds were prepared in an effort to have theultimate composition of the last three compounds approximate with, oridentical to, that of the first compound, in terms of structural units;

Needless to'say, as has been pointed out already, such resemblance isonly superficial for the reason that, depending on the temperature ofreaction, order in which reactants are added, and the very nature of thepossible reactions themselves, one does obtain products which areinherently and intrinsically difierent in molecular structure, size ofmolecule, etc.

It is well to recall that the use of compounds of the kind hereindescribed for the purposes involving surface activity, particularlydemulsification, does not involve chemical reactivity in the ordinarysense. Surface activity, and particularly surface aotivityphenomena asexemplified by'demulsifica-tion, is concerned with the actual shapes andsizes of molecules. Such concept, even though obscure and difficult todefine, acquires a large degree of reality and value in an invention ofthe kind herein specified even though it is difficult to set forth suchqualities in measures which are more concise and specific than thosewhich have been included.

Only a few examples need be repeated at this point to emphasize thesedifi'erences which, in our opinion, are related to the sizes, shapes,and

associated of molecules, and especially at interfaces. If phthalatedcastor oil is reacted with ethylene oxide, one builds up -a derivativeof the type in which there is always a residual hydroxyl for the reasonthat ethylene oxide acts like a monofunctional reactant. If onesubstitutes a glycol for ethylene oxide, then one is employing adifunctional reactant, and one mole of a glycol can act as a couplingreagent to unite two moles of phthalated .castor oil. Likewise, with theglycol and a glyceride, or any ester including a phthalated acidester,.alcoholysis can and usually does take place, particularly atelevated temperatures. This is not true in the case of ethylene oxide. 7

' ulif i i d P 1: Identifying Per cent of g y at can Per cent ical mfinal glycerol resx 5 Reactants and how made igfzg gfig product idue infinal ggg' g 3%,

pound final product f 3 835 3 I product L--24633. Castor oil plus 2%moles phth. anhyd. (135 C.) 33.2 12.0 1. 75 51.5

to give acid ester plus Ethylene Oxide (140 0.).

L24645 Castor oil plus 2% moles phth. anhyd. plus poly- 32. 4 11.7 1. 7053. 7

glycol, M. W. 1540 (235 0.).

L-24646 Polyglycol, M. W. 1540, .8 mole plus phthalic 31. 2 13. 1 1.6452.8

anhyd. 1.6 mole plus castor oil .8. The polyglycol plus anhyd. heateduntil acid v. drops to of orig. The castor oil is added and heated againfor 2 hrs. at 250 C. L24650. Castor oil plus 2% moles phth. anhyd. (135C.) 31.4 11.3 1.05 i 53.1

plus polyglycol 770.

In examining the above table it will be noted all radicals shown do notadd to quite 100%. The reason is that some connective oxygen atoms arenot included, particularly those attached to glycerol and that, in someinstances, there may have been elimination of Water Which affected thefinal percentage.

Attention is directed to the. fact again that L-24633 typifies one ofthe compounds described herein. In L-24645 the same intermediate(phthalated castor oil) was reacted with a polyethyleneglycol having amolecular weight of 1540, so as to give a compound which is analogous asfar as its structural parts are concerned, as in the case of 11-24633.In 1 -24646 the polyglycol was first combined with a phthalic anhydrideand reacted with a castor oil in a manner decribed in the series ofpatents previously referred to, to wit, U. S. Patents Nos. 2,295,163through 2,295,170. was substantially the same as in L-24645, to wit, theintermediate was the same as in 11-24633 (phthalated castor oil), butinstead of using a mole of a polyethyleneglycol having a molecularweight of 1540, there was used instead two moles In compound L-24640 theprocedure This .is illustrated by noting the comparative wettingefl'l'ciencies (which properly in turn are related to surface activity)in the case of some of the simpler polyglycol fatty acids and a selectedalkoxy derivatives.

of polyethyleneglycol having a molecular weight y l In addition to thefour compounds above described, i. e., one derived by the use ofethylene oxide and the others by the use of a polyethyleneglycol, it isobvious that other compounds could be made, including the use of analkoxy polyethyleneglycol. For instance, one could introduce a residuefrom a monohydric alcohol, such as methyl alcohol, ethyl alcohol, orpropyl alcohol, etc., into a glycol. Such alkyl radical is introducedrather easily by simply substituting the monohydric alkyl ether of aglycol for the dihydric glycol. A suitable compound could be obtained bytreating methyl or ethyl alcohol with ethylene oxide so as to give anether glycol having a single hydroxyl and a molecular Weight com parableto the molecular Weight of the glycol previously described, that is, 770and 1540.

Concentration (g. per cc.) for 25 sec. wet- Wetting Agent ting at 25 0.

Demulsifymg test 4 1 Date of test April 2 1948 State ol' California 011field-l Montebello Oil company Century Lease 4. Repetto Well No. 15

Per cent emulsion in fluid from Well.-. Per cent free water in fluidfrom well Per cent water obtained by complete demulsification 44 Per.cent demulsifier, in test solution Temperature of tests.'.- Period ofagitation after adding dexnulsifie Nature of agitation; machinewithshaker arm hakes per inute. Ratio of demulsifier to well fluid 1113,000;1:26,000 (see below See values in table 00 F.

April 2, 1948 Signal Hill L. Brown #1- Per cent free water in fluidfr'oih' well. L Per cent water obtained by completeidemulsificatzom 46Per cent demulsifier in test solutlon See values in table Temperatureoftests; 90 F.

Period of agitation after adding demulsifier Nature of agitation;machine with shaker at min. er minute 130 Ratio of demulsifier towell'fluid 1,13,000 l:26,000 (see below) L-24633 L-24645 L-24646 L-24656Per Cent Demflslfier 1/2e,ooo 1/13,000 1/13,000 1/13,000 Blank Time teststarted 1:20. cc. water out at 8 9 7 7 Trace 22 24 22 22 D0. 26 27 26 26D0. 31 2s 1 2s 30 Do. 31 28 28" 30 Do. 32 31 31 31 D0.

Demulszfymg test 6' Date'oftest April 2, 19i8 State of California Oilfield Seal Beach Oil compan Hellman Estates Lease; 3A WelL 3A Per centemulsion in fluidlr'oni well.

Per cent free water in fluid from wellu 6 Per cent water obtained bycomplete demulsification 16 Per cent demulsifier in test solution Seevalues in table Temperature of tests 0 Period of agitation after addingdemulsifier Nature of agitation; machine with shaker arm; u

Ratio of demulsifier to well fluid 1:l0,000 1:20,000 (see below) L-24633L-24645 L 24c46 L-24650 Per Gent Demflsfler 1120,0o0 1 1o,000 1 10,00o 110,0oo- Blank Time test started :20. cc. water out at-' I 1:20 (4/2) 1010 8 8 Trace n45 (4 2)-. 12 11 10 11 Do. 12135 13 11 11 12, Do. 10:40 (413 12 11 12 Do. 10:55 (4/4)-; 13 13 13 Do.

7 In addition to the foregoing demulsifying tests, the samefourcompounds identified as ill-24633, 11-24645, L-24646 and L-24650,have been tested on other emulsions with comparable differences. Forsake of brevity these other tests are omitted but they include, amongothers, a test on an oil from Well No. 16, Cueller Lease oi CoxandHammond, in the I-Io'finian Pool, Alice, Texas; the Stanolind Oil & GasCompany composite sample from the battery from. a lease located in theWink Field near Kermit, Texas, etc.

These series of tests reveal that the compound obtained by the use ofethylene. oxide was 35% to 65 better in numerous instances, and notinfre'-' quently was 100% better.

What has been said previously in regard to the structure of compoundswhich appear to be analogous at first superficial examination, should bereconsidered in light ofthe previous descrip tion of 11-24633, L24645,L-24646, and 11-24650, together with the foregoing tests. The same sortsof differences would be shown in other comparable tests where surfaceactivity is-concerned with the industrial application; as for instance,break induction in doctor'treat'ment of sour hy- "drocarbons.'- The factthat there is a'similarity,

in fact, almost an identity of structure when I California;

measured in terms of acid radicals, ethylene oxide radicals, etc., doesnot mean that the size of molecules is the same for the obviousreasonthat the same materials of construction yield architecturally differentproducts.

In the" hereto appended claims the word water-miscible is employed todesignate a sol or solution which is permanent for either an indefiniteperiod of time;- or for such extended period of time as wouldunquestionably permit its utilization for the herein designated purposeswithout undue difiiculties.

The products herein described, andparticularly for use as demulsiiying.agents, may be considered as intermediates for further reaction. Forexample, they may be reacted, with chloroacetic acid or similar lowmolal alpha-halogenated carboxy acid to produce an ester. Such esterwill serve many of the purposes herein described, i. e.-, as ademulsifier, break inducer, etc. Such alpha-halogenated carboxy acidester may be reacted further, for example, with a tertiary amine, suchas dimethyldodecylamine, esterified triethanolamines in which the acylradical is derived from a detergent-forming monocarboxy acid, and fromhydroxylated amines obtained, for example, by reaction with high molalamines, such as octadecylamine with two moles of ethylene oxide. Suchcompounds or derivatives again can be employed for all of the variouspurposes herein indicated, and. particularly for demulsification.

The word miscible is. frequently used to mean soluble in allproportions. In a technical sense it is sometimes employed to meansoluble without necessarily meaning in all proportions, and suchsolubility may include a colloidal dispersion orv sol as well asmolecular solution. The Word water-miscible is employed in the heretoappended claims in this more restricted meaning.

Having thus described our invention, what we claim as new and desire tosecure by Letters Patent is: 7

1. A Water-miscible oxyethylated triricinolein acidic ester; saidtriricinolein acidic ester being that of a saturated di'carbox'y acidhaving not over 10' carbon atoms and characterized by the fact thatprior to oxyethylation there is present at least one dicarboxy' acidcarboxyl radical for each triricinolein radical, and all dicarboxy acidradicals are directly attached to the ricinoleyl radical.

2. A water-miscible oxyethylated triricinolein acidic ester; saidt'riri'cinolein acidic ester being that of a saturated dicarboxy acidhaving not over 10 carbon atoms and characterized by the fact that priorto oxyethylation there is present a plurality of dicarboxy acid carboxylradicals for each triricinolein radical, and all dicarboxy radi cals aredirectly attached to the ricinoleyl radical.

3. A water=miscible oxyethylated triricinolein acidic ester; saidtriricinolein acidic ester being that of a saturated dicarboxy acidhaving not over 10 carbon atoms and characterized by the fact that priorto oxyethylation there is present a plurality of dic'arboxy acidcarboxylradicals for each 'tririci'nolein radical, and all dicarboxyradicals are directly attached to the ricinoleyl radical; with thefurther-proviso that the weight of ethylene oxide added by reactionbased on the weight of the triricinolein acidic ester prior tooxyeth'ylation is within the range of to 1 25%.

4. A water-miscible triricinolein acidic ester; said triricinoleinacidic ester being that of plithal-ic acid and characterized by the factthat prior to oxyethylation there is present a pluralityof phthalic acidradicals for each triricinolein radical, and all phthalic acid radicalsare directly attached to the ricinoleyl radical; with the fur- 21 therproviso that the weight of ethylene oxide added by reaction based on theweight of the triricinolein acidic ester prior to oxyethylation iswithin the range of 75% to 125%.

5. A water-miscible triricinolein acidic ester; said triricinoleinacidic ester being that of adipic acid and characterized by the factthat prior to oxyethylation there is present a plurality of adipic acidradicals for each triricinolein radical, and all adipic acid radicalsare directly attached to the ricinoleyl radical; with the furtherproviso that the weight of ethylene oxide added by reaction based on theweight of the triricinolein acidic ester prior to oxyethylation iswithin the range of 75% to 125%.

6. A water-miscible triricinolein acidic ester; said triricinoleinacidic ester being that of diglycollic acid and characterized by thefact that prior to oxyethylation there is present a plurality ofdiglycollic acid radicals for each triricinolein 22 radical, and alldiglycollic acid radicals are directly attached to the ricinoleylradical; with the further proviso that the weight of ethylene oxideadded by reaction based on the weight of the triricinolein acidic esterprior to oxyethylation is within the range of to MELVIN DE GROOTE.

BERNHARD KEISER.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,081,266 Bruson May 25, 19372,295,168 De Groote Sept. 8, 1942 2,343,434 De Groote Mar. '7, 19442,353,695 De Groote July 18, 1944

1. A WATER-MISCIBLE OXYETHYLATED TRIRICINOLEIN ACIDIC ESTER; SAIDTRIRICINOLEIN ACIDIC ESTER BEING THAT OF A SATURATED DICARBOXY ACIDHAVING NOT OVER 10 CARBON ATOMS AND CHARACTERIZED BY THE FACT THAT PRIORTO OXYETHYLATION THERE IS PRESENT AT LEAST ONE DICARBOXY ACID CARBOXYLRADICAL FOR EACH TRIRICINOLEIN RADICAL, AND ALL DICARBOXY ACID RADICALSARE DIRECTLY ATTACHED TO THE RICINOLEYL RADICAL.